CN112876902A - Flame-retardant thermal expansion microcapsule and preparation method and application thereof - Google Patents
Flame-retardant thermal expansion microcapsule and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of flame-retardant materials, and particularly discloses a flame-retardant thermal expansion microcapsule as well as a preparation method and application thereof. The flame-retardant thermal expansion microcapsule comprises a core material and a wall material, wherein the wall material comprises alkyl diisocyanate, polyfunctional long-chain polyether amine and an amino-substituted mono-spiro phosphazene derivative, and the core material comprises a low-boiling-point alkane foaming agent. The microcapsule prepared by adopting the wall material and the core material as raw materials by adopting an interfacial polycondensation method has the average particle size of 1-3 mu m, the limited oxygen index of 27.7 percent and the foaming multiplying power of 7.6 times, can improve the three-dimensional effect of a printed product and the flame retardant property of the printed product when being applied to foaming ink, has simple and easy operation of the preparation method, does not contain halogen in a microcapsule system, does not cause pollution to the environment, and has good economic benefit and development prospect.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to a flame-retardant thermal expansion microcapsule and a preparation method and application thereof.
Background
Microencapsulation is a technique that uses a polymer or inorganic wall material to coat different phase materials to form a typical 'core-shell' structure. When the substance is coated, the compact shell material can perform good protection and fixation on the substance. The heat expansion microcapsule is prepared by coating organic solvents with different boiling points as foaming agent in thermoplastic polymer shell material with good toughness by microcapsule technology to form polymer particles with different sizes of 1-100 μm. When the heat-expandable microcapsules are heated, the foaming agent in the core vaporizes, and the resulting pressure causes the outer shell to expand, thereby increasing the volume of the microcapsules by several tens of times or more. The thermal expansion microcapsule has good thermal expansion performance, so the thermal expansion microcapsule can be applied to the field of foaming ink. When the paper, the fabric or the hard plane containing the ink of the heat expansion microcapsule is heated, the microcapsule expands and enlarges, so that the printed characters or patterns show a raised stereoscopic vision effect. The heat expansion microcapsule can increase the aesthetic feeling of printed matters, improve the quality of the printed matters and the technical level of ink application, and the development of related technologies is attracted by extensive attention in recent years.
However, since the thermal expansion microcapsule is composed of a polymer wall material and an organic foaming agent, both of which are inflammable substances, when the thermal expansion microcapsule is applied to the fields of paper, fabric and the like, particularly under the condition that expansion is caused by heating, fire is easily caused, and the safety of human life and property is harmed. Therefore, the flame retardant property of the thermal expansion microcapsule is improved, the multiple functions of the thermal expansion microcapsule are realized, and the method has very important significance for expanding the application field of the thermal expansion microcapsule.
Disclosure of Invention
Aiming at the problems that the thermal expansion microcapsule in the prior art does not have flame retardance or has poor flame retardance and needs to be further improved, the invention provides a flame-retardant microcapsule and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the flame-retardant thermal expansion microcapsule comprises a core material and a wall material, wherein the wall material comprises alkyl diisocyanate, polyfunctional long-chain polyether amine and an amino-substituted mono-spirocyclic phosphazene derivative, and the core material comprises a low-boiling-point alkane foaming agent.
Compared with the prior art, the microcapsule provided by the invention takes the low-boiling-point alkane foaming agent as the core and takes the alkyl diisocyanate-polyetheramine-unispiro phosphazene copolymer as the shell to form a typical core-shell structure thermal expansion microcapsule, wherein the polyurea shell formed by the alkyl diisocyanate and the polyetheramine not only can play an effective role in protecting the low-boiling-point alkane foaming agent at the core part and prevent the foaming agent from leaking and losing, but also can provide a larger expansion space for the foaming agent due to the characteristics of high toughness and high elasticity, and further introduces the cyclophosphazene derivative with the unispiro structure on the side chain of the polyurea molecule, so that the microcapsule is endowed with excellent flame retardant property on the premise of ensuring that the elasticity and the toughness property of the polyurea outer layer are not influenced, and the structural spiro structure and the benzene ring-like structure not only can obviously improve the heat resistance of the polyurea shell, the strength of the polyurea shell can be further improved, and the stability of the microscopic form and structure of the microcapsule can be further maintained after the microcapsule expands.
The flame-retardant thermal expansion microcapsule prepared by the invention has the advantages that the limited oxygen index can reach more than 26.5 percent, the foaming multiplying power can reach 7.6 times, good form stability and structural integrity can be maintained, the foaming performance is good, the flame retardant performance is excellent, halogen is not contained in a microcapsule system, the environment cannot be polluted or damaged, and the flame-retardant thermal expansion microcapsule has good economic benefit and development prospect.
Preferably, the low boiling alkane blowing agent comprises at least one of n-hexane, n-heptane, isopentane, or isooctane.
The preferred blowing agent increases the foaming properties of the microcapsules and lowers the foaming temperature so that the foaming temperature of the microcapsules is 90-150 ℃.
Preferably, the alkyl diisocyanate includes one or two of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.
Preferably, the multifunctional long-chain polyetheramine is a trifunctional long-chain polyetheramine having a molecular weight of 4000-7000 g/mol.
Preferably, the amido-substituted mono-spirocyclic phosphazene derivative is 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene.
The preferable wall material is favorable for forming the wall material with high elasticity, high toughness, high polymerization degree and good stability, not only ensures that the shell layer has better compactness and integrity, can better protect the core material, but also improves larger expansion space for the foaming agent, is favorable for improving the foaming multiplying power, improves the structural stability of the expanded microcapsule and is favorable for keeping the complete form of the microcapsule.
The invention also provides a preparation method of the flame-retardant thermal expansion microcapsule, which at least comprises the following steps:
step one, adding the low-boiling-point alkane foaming agent, alkyl diisocyanate, cationic surfactant and nucleating agent into water under inert atmosphere, and stirring and mixing uniformly to obtain an oil-in-water emulsion;
step two, adding the multifunctional long-chain polyether amine and the amino-substituted mono-spiro phosphazene derivative into an organic solvent, and stirring and mixing uniformly to obtain a mixed solution;
and thirdly, heating the oil-in-water emulsion to 60-80 ℃ under inert atmosphere, then dropwise adding the mixed solution, keeping the temperature and stirring for 7-12h after dropwise adding, filtering, washing and drying to obtain the flame-retardant thermal expansion microcapsule.
The flame-retardant thermal expansion microcapsule with a core-shell structure is prepared by an interfacial polycondensation method, wherein the polyurea layer with high toughness not only can provide effective isolation and protection for a foaming agent, but also can provide a larger expansion space for the foaming agent, and the amino substituted mono-spiro phosphazene derivative with flame-retardant property is introduced into polyurea, so that the flame-retardant property of the microcapsule can be improved, the defect of flammability of a high-molecular shell material is overcome, the strength of a shell layer can be improved, and the structural stability of the expanded microcapsule is improved. And no toxic and harmful substances are generated in the reaction process, the preparation process is simple and easy to control, the industrial production is easy to realize, and the method has high popularization value.
Preferably, in the first step, the cationic surfactant is one of cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride, dioctadecyl amine hydrochloride, N-dimethyloctadecyl amine hydrochloride or octadecyldimethylbenzylammonium chloride.
Preferably, in the first step, the nucleating agent is ammonium chloride.
Preferably, in the second step, the organic solvent is tetrahydrofuran, dioxane, acetonitrile or dichloromethane.
In the present invention, the amount of water used in the first step and the amount of the organic solvent used in the second step are not limited to the amount that does not affect the reaction, and are generally about 10 times the mass of the reaction raw materials.
Optionally, in the step one, water is 10 times of the mass of the low-boiling-point alkane foaming agent; in the second step, the volume-mass ratio of the organic solvent to the multifunctional long-chain polyether amine is 10:1, wherein the volume unit is milliliter, and the mass unit is gram.
Preferably, in the first step, the stirring speed is 500-700rpm, and the stirring time is 2-4 h.
Preferably, in the third step, the dropping time is 1-3 h.
Preferably, the mass percentages of the reactants are as follows: 25.0-30.0% of low-boiling-point alkane foaming agent, 25.0-30.0% of alkyl diisocyanate, 20.0-25.0% of polyfunctional long-chain polyetheramine, 20.0-25.0% of amino-substituted mono-spiro phosphazene derivative, 2.0-2.5% of cationic surfactant and 0.2-0.3% of nucleating agent.
The preferred reaction conditions are favorable for obtaining microcapsules with the average particle size of 1-3 mu m.
Taking trifunctional long-chain polyether amine and toluene diisocyanate as examples, the reaction equation is as follows:
r in the above formula is phenyl; r1、R2Being alkanes of different chain lengths, n1、n2Is a natural number of 1 to n, R3、R4、R5And R6Is polyurea molecular chain segment with different polymerization degrees formed by the reaction of long-chain polyether amine and toluene diisocyanate.
Preferably, the preparation method of the amino-substituted mono-spirocyclic phosphazene derivative comprises the following steps:
step a, adding hexachlorocyclotriphosphazene into dichloromethane in inert atmosphere, uniformly mixing, adding ethylenediamine, stirring at the temperature of 0-5 ℃ at the speed of 200-400rpm for 1-3h, filtering, washing and drying to obtain disubstituted tetrachlorocyclotriphosphazene, namely 1, 1-ethylenediamine-3, 3,5, 5-tetrachlorocyclotriphosphazene; the reaction equation is as follows:
b, adding tetrabutylammonium bromide, sodium hydroxide and a phenol or alcohol compound into deionized water, uniformly mixing, then adding a dichloromethane solution of the disubstituted tetrachlorocyclotriphosphazene, stirring for 24-36h under the condition of 200-400rpm, filtering, washing, drying and separating by column chromatography to obtain the amino-substituted mono-spiro phosphazene derivative; the reaction equation is as follows:
preferably, the molar ratio of the hexachlorocyclotriphosphazene to the ethylenediamine is 1: 1.9-2.3.
Preferably, the molar ratio of the tetrabutylammonium bromide to the sodium hydroxide to the phenolic or alcoholic compound to the disubstituted tetrachlorocyclotriphosphazene is (0.03-0.05): (8-10): (4-6): 1.
Preferably, the phenolic compound is phenol, p-cresol; the alcohol compound is methanol, ethanol, propanol or n-butanol.
Optionally, the amount of dichloromethane used in step a is not limited to affect the reaction, and is generally about 10 times the mass of the reaction raw materials. The dosage of the deionized water in the step b is about 30 times of the mass of the phenols or the alcohols compounds.
Preferably, the chromatographic solution for column chromatography is a mixed solution of tetrahydrofuran and petroleum ether with a volume ratio of 1: 4.
The inert atmosphere in the invention is provided by inert gas, and the inert gas can be nitrogen, argon and the like.
The invention also provides application of any one of the flame-retardant thermal expansion microcapsules in the field of foaming ink.
The flame-retardant microcapsule prepared by the invention has small particle size (1-3 mu m), high foaming ratio and good flame-retardant property, can provide visual and tactile 3D concave-convex three-dimensional effect when being applied to printing ink, has excellent flame-retardant property, can generate good flame-retardant effect when a fire breaks out, prevents the fire from spreading, has high strength of the wall of the microcapsule and good heat resistance, can not leak out as long as the temperature is not more than 280 plus one temperature and 300 ℃, can further prevent the fire from spreading caused by the leakage of the foaming agent, does not contain halogen in the wall material, and cannot generate the problem of environmental pollution, is an environment-friendly heat-expansion flame-retardant microcapsule, and greatly widens the application range of the heat-expansion microcapsule.
The addition amount of the flame-retardant thermal expansion microcapsule provided by the invention in the foaming ink is 5-20 wt%.
The thermal expansion microcapsule prepared by the invention is added into the foaming ink in a small amount, so that good flame retardant property can be achieved, a printed matter can show a prominent 3D (three-dimensional) effect after being heated, the requirements of product functionality and attractiveness can be met, and the thermal expansion microcapsule is very suitable for being applied to the field of foaming ink.
Drawings
FIG. 1 is a chart of the infrared spectrum of 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene prepared in example 1 of the present invention;
FIG. 2 is an electron scanning electron microscope image of the flame retardant thermal expansion microcapsule prepared in example 1 of the present invention before expansion;
fig. 3 is an electron scanning electron microscope image of the expanded thermal expansion microcapsule prepared in comparative example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment of the invention provides a flame-retardant thermal expansion microcapsule, and a preparation method of the microcapsule comprises the following steps:
step one, preparing an amino-substituted mono-spiro phosphazene derivative:
adding 20.0g of hexachlorocyclotriphosphazene and 200mL of dichloromethane into a three-opening reaction bottle under the condition of nitrogen protection, uniformly mixing, then adding 6.9g of ethylenediamine, stirring for 2h at the stirring speed of 300rpm under the condition of ice bath, filtering, washing with deionized water and saturated salt solution for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration and spin drying to obtain disubstituted tetrachlorocyclotriphosphazene, namely 1, 1-ethylenediamine-3, 3,5, 5-tetrachlorocyclotriphosphazene;
under the protection of nitrogen, adding 0.48g of tetrabutylammonium bromide, 11.9g of sodium hydroxide, 14.1g of phenol and 400mL of deionized water into a three-mouth reaction bottle, uniformly mixing, then dropwise adding the disubstituted tetrachlorocyclotriphosphazene solution (10.0g of disubstituted tetrachlorocyclotriphosphazene is dissolved in 200mL of dichloromethane), wherein the dropwise adding time is 2h, after the dropwise adding is finished, stirring at the room temperature for 24h at the speed of 300rpm, filtering, washing with deionized water and saturated saline water for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration and spin drying, and then carrying out column chromatography (petroleum ether: tetrahydrofuran ═ 4:1) separation to obtain an amino-substituted mono-spiro phosphazene derivative, namely 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene;
step two, under the protection of nitrogen, adding 25.0g of isopentane foaming agent and 25.0g of toluene diisocyanate into a three-opening reaction bottle, uniformly mixing, then adding 250mL of deionized water, 10mL of acetone, 0.2g of ammonium chloride and 2.0g of hexadecyl trimethyl ammonium bromide, and stirring at room temperature at the speed of 500rpm for 2 hours to obtain a stable and uniform oil-in-water emulsion;
step three, mixing 20.0g of trifunctional long-chain polyether amine with the molecular weight of 4000-7000 g/mol, 24.0g of the prepared amino-substituted mono-spiro phosphazene derivative and 200mL of dichloromethane uniformly to obtain a mixed oil phase solution;
and step four, heating the three-mouth reaction bottle in the step two to 65 ℃, dropwise adding the prepared mixed oil phase solution for 2 hours, keeping the temperature and continuously stirring for 10 hours after dropwise adding, filtering, washing with deionized water and alcohol for 2-3 times respectively, and drying at room temperature until the washing solution is completely volatilized to obtain the flame-retardant thermal expansion microcapsule.
The infrared spectrogram of the amino-substituted mono-spirocyclic phosphazene derivative prepared in the embodiment, namely 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene is shown in figure 1, and the chemical structure of the amino-substituted mono-spirocyclic phosphazene derivative is confirmed by corresponding characteristic peaks.
An electron scanning microscope picture of the flame-retardant thermal expansion microcapsule prepared in the embodiment before foaming and expansion is shown in fig. 2, and it can be seen from the picture that the average particle size of the microcapsule is 1-3 μm, the size is uniform, and the morphology before foaming and expansion is regular.
Testing the foaming performance of the heat-expandable microcapsule: measured by a thermo-mechanical analyzer TMA Q-400 manufactured by TA Instrument Co. The specific operation is as follows: placing TMA test position in quartz crucible with inner diameter of 3.4mm and depth of 14.2mm, setting zero position, placing 1.0mg thermal expansion microcapsule in the crucible, reading probe initial height, increasing sample temperature from ambient temperature to 230 deg.C at 20 deg.C/min, applying 0.06N force by the probe, analyzing by measuring probe vertical displacement to obtain initial foaming temperature Ts(temperature at which probe displacement starts to increase), maximum foaming temperature Tm(temperature at which probe displacement reaches maximum), the minimum bubble density ρ was calculated by testingminAnd initial density of microspheres ρ0The expansion ratio of the microspheres is calculated as rho0/ρmin。
The test results show that the initial foaming temperature of the microcapsules prepared in the embodiment is 100 ℃, the temperature at which the expansion reaches the maximum is 135 ℃, and the foaming ratio is 7.6 times.
Example 2
The embodiment of the invention provides a flame-retardant thermal expansion microcapsule, and a preparation method of the microcapsule comprises the following steps:
step one, preparing an amino-substituted mono-spiro phosphazene derivative:
adding 19.5g of hexachlorocyclotriphosphazene and 220mL of dichloromethane into a three-opening reaction bottle under the condition of nitrogen protection, uniformly mixing, then adding 7.6g of ethylenediamine, stirring for 3h at a stirring speed of 200rpm under the condition of ice bath, filtering, washing with deionized water and saturated salt solution for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain disubstituted tetrachlorocyclotriphosphazene, namely 1, 1-ethylenediamine-3, 3,5, 5-tetrachlorocyclotriphosphazene;
adding 0.48g of tetrabutylammonium bromide, 10.8g of sodium hydroxide, 8.2g of ethanol and 300mL of deionized water into a three-mouth reaction bottle under the protection of nitrogen, uniformly mixing, then dropwise adding the disubstituted tetrachlorocyclotriphosphazene solution (10.0g of disubstituted tetrachlorocyclotriphosphazene is dissolved in 200mL of dichloromethane), wherein the dropwise adding time is 2h, stirring at the room temperature for 30h at the speed of 200rpm after the dropwise adding is finished, filtering, washing with deionized water and saturated saline water for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration and spin drying, and then carrying out column chromatography (petroleum ether: tetrahydrofuran ═ 4:1) separation to obtain an amino-substituted mono-spirocyclic phosphazene derivative, namely 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene;
step two, under the protection of nitrogen, adding 29.0g of n-heptane foaming agent and 29.0g of isophorone diisocyanate into a three-mouth reaction bottle, uniformly mixing, then adding 300mL of deionized water, 10mL of acetone, 0.3g of ammonium chloride and 2.1g of hexadecyl trimethyl ammonium bromide, and stirring at the speed of 600rpm for 3 hours at room temperature to obtain a stable and uniform oil-in-water emulsion;
step three, mixing 25.0g of trifunctional long-chain polyether amine with the molecular weight of 4000-7000 g/mol, 20.0g of the prepared amino-substituted mono-spiro phosphazene derivative and 220mL of dichloromethane uniformly to obtain a mixed oil phase solution;
and step four, heating the three-mouth reaction bottle in the step two to 75 ℃, dropwise adding the prepared mixed oil phase solution for 2.5 hours, keeping the temperature and continuously stirring for 12 hours after dropwise adding is finished, filtering, washing with deionized water and alcohol for 2-3 times respectively, and drying at room temperature until the washing solution is completely volatilized to obtain the flame-retardant thermal expansion microcapsule.
Example 3
The embodiment of the invention provides a flame-retardant thermal expansion microcapsule, and a preparation method of the microcapsule comprises the following steps:
step one, preparing an amino-substituted mono-spiro phosphazene derivative:
adding 19.0g of hexachlorocyclotriphosphazene and 200mL of dichloromethane into a three-opening reaction bottle under the condition of nitrogen protection, uniformly mixing, then adding 6.2g of ethylenediamine, stirring for 1h at a stirring speed of 400rpm under the condition of ice bath, filtering, washing with deionized water and saturated salt solution for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain disubstituted tetrachlorocyclotriphosphazene, namely 1, 1-ethylenediamine-3, 3,5, 5-tetrachlorocyclotriphosphazene;
adding 0.39g of tetrabutylammonium bromide, 9.6g of sodium hydroxide, 12.9g of p-cresol and 300mL of deionized water into a three-mouth reaction bottle under the protection of nitrogen, uniformly mixing, then dropwise adding the disubstituted tetrachlorocyclotriphosphazene solution (10.0g of disubstituted tetrachlorocyclotriphosphazene is dissolved in 200mL of dichloromethane), wherein the dropwise adding time is 2h, stirring at the speed of 400rpm for 24h at room temperature after dropwise adding is finished, filtering, washing with deionized water and saturated saline water for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration, spin drying, and then carrying out column chromatography (petroleum ether: tetrahydrofuran ═ 4:1) separation to obtain an amino-substituted mono-spirocyclic phosphazene derivative, namely 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene;
step two, under the protection of nitrogen, adding 26.0g of isooctane foaming agent and 26.0g of diphenylmethane diisocyanate into a three-opening reaction bottle, uniformly mixing, then adding 260mL of deionized water, 8mL of acetone, 0.2g of ammonium chloride and 2.3g of dioctadecyl amine hydrochloride, and stirring at room temperature at the speed of 500rpm for 2 hours to obtain a stable and uniform oil-in-water emulsion;
step three, mixing 24.0g of trifunctional long-chain polyether amine with the molecular weight of 4000-7000 g/mol, 24.0g of the prepared amino-substituted mono-spiro phosphazene derivative and 230mL of dichloromethane uniformly to obtain a mixed oil phase solution;
and step four, heating the three-mouth reaction bottle in the step two to 65 ℃, dropwise adding the prepared mixed oil phase solution for 2 hours, keeping the temperature and continuously stirring for 10 hours after dropwise adding, filtering, washing with deionized water and alcohol for 2-3 times respectively, and drying at room temperature until the washing solution is completely volatilized to obtain the flame-retardant thermal expansion microcapsule.
Example 4
The embodiment of the invention provides a flame-retardant thermal expansion microcapsule, and a preparation method of the microcapsule comprises the following steps:
step one, preparing an amino-substituted mono-spiro phosphazene derivative:
adding 19.1g of hexachlorocyclotriphosphazene and 220mL of dichloromethane into a three-opening reaction bottle under the condition of nitrogen protection, uniformly mixing, then adding 6.9g of ethylenediamine, stirring for 3h at a stirring speed of 400rpm under the condition of ice bath, filtering, washing with deionized water and saturated salt solution for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration, and carrying out spin drying to obtain disubstituted tetrachlorocyclotriphosphazene, namely 1, 1-ethylenediamine-3, 3,5, 5-tetrachlorocyclotriphosphazene;
adding 0.34g of tetrabutylammonium bromide, 11.7g of sodium hydroxide, 5.3g of methanol and 310mL of deionized water into a three-mouth reaction bottle under the protection of nitrogen, uniformly mixing, then dropwise adding the disubstituted tetrachlorocyclotriphosphazene solution (10.0g of disubstituted tetrachlorocyclotriphosphazene is dissolved in 200mL of dichloromethane), wherein the dropwise adding time is 2h, stirring at the room temperature for 30h at the speed of 200rpm after the dropwise adding is finished, filtering, washing with deionized water and saturated saline water for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration and spin drying, and then carrying out column chromatography (petroleum ether: tetrahydrofuran ═ 4:1) separation to obtain an amino-substituted mono-spirocyclic phosphazene derivative, namely 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene;
step two, under the protection of nitrogen, adding 25.0g of n-hexane foaming agent and 25.0g of hexamethylene diisocyanate into a three-mouth reaction bottle, uniformly mixing, then adding 220mL of deionized water, 9mL of acetone, 0.22g of ammonium chloride and 2.4g of octadecyl dimethyl benzyl ammonium chloride, and stirring at the speed of 550rpm for 2.5 hours at room temperature to obtain a stable and uniform oil-in-water emulsion;
step three, mixing 22.0g of trifunctional long-chain polyether amine with the molecular weight of 4000-7000 g/mol, 24.0g of the prepared amino-substituted mono-spiro phosphazene derivative and 220mL of dichloromethane uniformly to obtain a mixed oil phase solution;
and step four, heating the three-mouth reaction bottle in the step two to 68 ℃, dropwise adding the prepared mixed oil phase solution for 3 hours, keeping the temperature and continuously stirring for 8 hours after the dropwise adding is finished, filtering, washing with deionized water and alcohol for 2-3 times respectively, and drying at room temperature until the washing solution is completely volatilized to obtain the flame-retardant thermal expansion microcapsule.
Example 5
The embodiment of the invention provides a flame-retardant thermal expansion microcapsule, and a preparation method of the microcapsule comprises the following steps:
step one, preparing an amino-substituted mono-spiro phosphazene derivative:
adding 21.0g of hexachlorocyclotriphosphazene and 210mL of dichloromethane into a three-opening reaction bottle under the condition of nitrogen protection, uniformly mixing, then adding 7.2g of ethylenediamine, stirring for 3h at the stirring speed of 300rpm under the condition of ice bath, filtering, washing with deionized water and saturated salt solution for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration and spin drying to obtain disubstituted tetrachlorocyclotriphosphazene, namely 1, 1-ethylenediamine-3, 3,5, 5-tetrachlorocyclotriphosphazene;
adding 0.44g of tetrabutylammonium bromide, 11.1g of sodium hydroxide, 10.4g of n-propanol and 330mL of deionized water into a three-mouth reaction bottle under the condition of nitrogen protection, uniformly mixing, then dropwise adding the disubstituted tetrachlorocyclotriphosphazene solution (10.0g of disubstituted tetrachlorocyclotriphosphazene is dissolved in 220mL of dichloromethane), wherein the dropwise adding time is 2.5h, stirring at the room temperature at the speed of 300rpm after dropwise adding is finished, filtering, washing with deionized water and saturated saline water for 2-3 times respectively, drying with anhydrous magnesium sulfate, carrying out suction filtration, spin drying, and then carrying out column chromatography (petroleum ether: tetrahydrofuran ═ 4:1) separation to obtain an amino substituted mono-spiro phosphazene derivative, namely 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene;
step two, under the protection of nitrogen, adding 27.0g of isopentane foaming agent and 27.0g of lysine diisocyanate into a three-opening reaction bottle, uniformly mixing, then adding 230mL of deionized water, 8mL of acetone, 0.23g of ammonium chloride and 2.1g N, N-dimethyl octadecylamine hydrochloride, and stirring at room temperature at 540rpm for 2 hours to obtain a stable and uniform oil-in-water emulsion;
step three, mixing 23.0g of trifunctional long-chain polyether amine with the molecular weight of 4000-7000 g/mol, 24.0g of the prepared amino-substituted mono-spiro phosphazene derivative and 250mL of dichloromethane uniformly to obtain a mixed oil phase solution;
and step four, heating the three-mouth reaction bottle in the step two to 78 ℃, dropwise adding the prepared mixed oil phase solution for 2 hours, keeping the temperature and continuously stirring for 12 hours after dropwise adding, filtering, washing with deionized water and alcohol for 2-3 times respectively, and drying at room temperature until the washing solution is completely volatilized to obtain the flame-retardant thermal expansion microcapsule.
Comparative example 1
This comparative example provides a thermally expandable microcapsule prepared exactly the same as example 1 except that 1, 1-ethylenediamine-3, 3,5, 5-tetraphenyloxycyclotriphosphazene was not added during the preparation.
Comparative example 2
This comparative example provides a thermally expandable microcapsule prepared exactly the same as example 1 except that 1, 1-ethylenediamine-3, 3,5, 5-tetraphenyloxycyclotriphosphazene was replaced with the same amount of trimeric O, O-2-spirocyclic phenylphosphonothioic acid diester trimethylene phosphazene during the preparation.
The microcapsules prepared in the comparative example are heated at 120 ℃, the microcapsules are heated by direct contact of an electric heating plate, an electron scanning microscope picture after the microcapsules are foamed and expanded is shown in figure 3, and analysis according to the scanning electron microscope picture shows that the microcapsules prepared in the comparative example have some collapse and deformation after being expanded, and the fact that the wall material added with the amido substituted mono-spiro phosphazene derivative has higher mechanical strength and is not easy to collapse and deform compared with other spiro phosphazene derivatives is proved, so that the form stability and the structural integrity of the microcapsules after thermal expansion can be obviously guaranteed.
The thermal expansion microcapsules prepared in examples 1 to 5 and comparative examples 1 to 2 were tested for flame retardancy according to the GB/T23864 standard, and the results are shown in Table 1.
TABLE 1 comparison of Properties
| Examples | Limiting oxygen index (%) |
| Example 1 | 27.7 |
| Example 2 | 26.5 |
| Example 3 | 27.3 |
| Example 4 | 27.4 |
| Example 5 | 27.1 |
| Comparative example 1 | 22.8 |
| Comparative example 2 | 23.5 |
Examples 2 to 5 described above all achieved substantially equivalent foaming properties to example 1.
If the foaming height of the ink is too high, it shows poor adhesion of the microcapsules to the ink, and thus, the adhesion of the thermally-expansible microcapsules prepared in the examples of the present invention to the ink was tested as follows. The formula of the ink is as follows:
printing virgin pulp (50 wt%), water-based acrylic resin (25 wt%), water (5 wt%), color paste (9 wt%), thermal expansion microcapsules (10 wt%), defoaming agent (0.2 wt%) and flatting agent (0.8 wt%). The raw materials are prepared into the ink according to the conventional ink preparation method.
The adhesion was rated according to ISO 12944 international standards (level 0 indicating a completely smooth cut edge with no one off, level 1 indicating a little coating off at the intersection and no significant more than 5% affected area, level 2 indicating a coating off at or along the cut edge and 5-15% affected area) using a cross-hatch spacing of 2 mm.
Test results show that the adhesive force between the thermal expansion microcapsules prepared in the embodiments 1 to 5 of the invention and the ink can reach 0 to 1 grade.
In the above test, the additives in the ink, such as the defoaming agent and the leveling agent, can be conventional substances in the field of ink, and the difference in the types of the substances does not have obvious influence on the adhesion test result.
In conclusion, the flame-retardant microcapsule prepared by the invention has the limit oxygen combustion index of 27.7%, the vertical combustion index of V-0 level and the foaming multiplying power of 7.6 times, and when the microcapsule is applied to foaming ink, the three-dimensional effect of a printed product can be improved, the flame-retardant performance of the printed product can also be improved, the preparation method is simple, convenient and feasible to operate, low in cost, green and environment-friendly, and meanwhile, the microcapsule system does not contain halogen, does not cause pollution to the environment, and has good economic benefits and development prospects.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The flame-retardant thermal expansion microcapsule comprises a core material and a wall material, and is characterized in that the wall material comprises alkyl diisocyanate, polyfunctional long-chain polyether amine and an amino-substituted mono-spiro phosphazene derivative, and the core material comprises a low-boiling-point alkane foaming agent.
2. The flame retardant thermal expansion microcapsule according to claim 1, wherein the low boiling point alkane blowing agent comprises at least one of n-hexane, n-heptane, isopentane, or isooctane.
3. The flame retardant thermal expansion microcapsule according to claim 1, wherein said alkyl diisocyanate comprises one or both of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.
4. The flame retardant thermal expansion microcapsule according to claim 1, wherein said multifunctional long-chain polyetheramine is a trifunctional long-chain polyetheramine having a molecular weight of 4000-7000 g/mol; and/or
The amido substituted mono-spiro phosphazene derivative is 1, 1-ethylenediamine-3, 3,5, 5-tetraphenoxy cyclotriphosphazene.
5. The process for preparing the flame retardant thermal expansion microcapsule according to any one of claims 1 to 4, comprising the steps of:
step one, adding the low-boiling-point alkane foaming agent, alkyl diisocyanate, cationic surfactant and nucleating agent into water under inert atmosphere, and stirring and mixing uniformly to obtain an oil-in-water emulsion;
step two, adding the multifunctional long-chain polyether amine and the amino-substituted mono-spiro phosphazene derivative into an organic solvent, and stirring and mixing uniformly to obtain a mixed solution;
and thirdly, heating the oil-in-water emulsion to 60-80 ℃ under inert atmosphere, then dropwise adding the mixed solution, keeping the temperature and stirring for 7-12h after dropwise adding, filtering, washing and drying to obtain the flame-retardant thermal expansion microcapsule.
6. The method for preparing the flame-retardant thermal expansion microcapsule according to claim 5, wherein in the first step, the cationic surfactant is one of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dioctadecylamine hydrochloride, N-dimethyloctadecylamine hydrochloride, or octadecyldimethylbenzylammonium chloride; and/or
In the first step, the nucleating agent is ammonium chloride; and/or
In the second step, the organic solvent is tetrahydrofuran, dioxane, acetonitrile or dichloromethane.
7. The preparation method of the flame-retardant thermal expansion microcapsule according to claim 5, wherein in the first step, the stirring speed is 500-700rpm, and the stirring time is 2-4 h; and/or
In the third step, the dripping time is 1-3 h.
8. The preparation method of the flame-retardant thermal expansion microcapsule according to claim 5, wherein the mass percentages of the reactants are as follows: 25.0-30.0% of low-boiling-point alkane foaming agent, 25.0-30.0% of alkyl diisocyanate, 20.0-25.0% of polyfunctional long-chain polyetheramine, 20.0-25.0% of amino-substituted mono-spiro phosphazene derivative, 2.0-2.5% of cationic surfactant and 0.2-0.3% of nucleating agent.
9. The method for preparing the flame-retardant thermal expansion microcapsule according to any one of claims 5 to 8, wherein the method for preparing the amine-substituted mono-spirocyclic phosphazene derivative comprises the steps of: under inert atmosphere, adding hexachlorocyclotriphosphazene into dichloromethane, mixing uniformly, adding ethylenediamine, stirring at 0-5 ℃ and 400rpm for 1-3h, filtering, washing and drying to obtain disubstituted tetrachlorocyclotriphosphazene;
adding tetrabutylammonium bromide, sodium hydroxide and a phenol or alcohol compound into deionized water, uniformly mixing, then adding a dichloromethane solution of the disubstituted tetrachlorocyclotriphosphazene, stirring for 24-36h under the condition of 200-400rpm, filtering, washing, drying, and performing column chromatography separation to obtain the amino-substituted mono-spiro phosphazene derivative.
10. The flame retardant thermal expansion microcapsule according to any one of claims 1 to 4, for use in the field of foaming inks.
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| GB1031020A (en) * | 1963-12-09 | 1966-05-25 | Shell Int Research | Improvements in or relating to polyurethanes |
| CN1446120A (en) * | 2000-06-05 | 2003-10-01 | 辛甄塔有限公司 | Novel microcapsules |
| CN107955162A (en) * | 2017-11-29 | 2018-04-24 | 广东聚航新材料研究院有限公司 | A kind of halogen-free flameproof, high working property PA6T polyamides and preparation method thereof |
| CN109232962A (en) * | 2018-08-29 | 2019-01-18 | 常州大学 | It is a kind of using polyurethane as the preparation method of the blowing microcapsule of wall material |
| CN109666333A (en) * | 2019-01-18 | 2019-04-23 | 北京印刷学院 | Thermal expansion type microcapsules and preparation method thereof, aqueous, environmental protective foam ink and its preparation method and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1031020A (en) * | 1963-12-09 | 1966-05-25 | Shell Int Research | Improvements in or relating to polyurethanes |
| CN1446120A (en) * | 2000-06-05 | 2003-10-01 | 辛甄塔有限公司 | Novel microcapsules |
| CN107955162A (en) * | 2017-11-29 | 2018-04-24 | 广东聚航新材料研究院有限公司 | A kind of halogen-free flameproof, high working property PA6T polyamides and preparation method thereof |
| CN109232962A (en) * | 2018-08-29 | 2019-01-18 | 常州大学 | It is a kind of using polyurethane as the preparation method of the blowing microcapsule of wall material |
| CN109666333A (en) * | 2019-01-18 | 2019-04-23 | 北京印刷学院 | Thermal expansion type microcapsules and preparation method thereof, aqueous, environmental protective foam ink and its preparation method and application |
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